Assessing the Accuracy of New Geminal-Based Approaches

We present a systematic theoretical study on the dissociation of diatomic molecules and their spectroscopic constants using our recently presented geminal-based wave function ansätze. Specifically, the performance of the antisymmetric product of rank two geminals (APr2G), the antisymmetric product...

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Bibliographic Details
Published inThe journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 118; no. 39; pp. 9058 - 9068
Main Authors Tecmer, Paweł, Boguslawski, Katharina, Johnson, Paul A, Limacher, Peter A, Chan, Matthew, Verstraelen, Toon, Ayers, Paul W
Format Journal Article
LanguageEnglish
Published United States American Chemical Society 02.10.2014
Subjects
Accuracy
Bonding
Computational efficiency
Constants
Diatomic molecules
Spectroscopy
Wave functions
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Summary:We present a systematic theoretical study on the dissociation of diatomic molecules and their spectroscopic constants using our recently presented geminal-based wave function ansätze. Specifically, the performance of the antisymmetric product of rank two geminals (APr2G), the antisymmetric product of 1-reference-orbital geminals (AP1roG) and its orbital-optimized variant (OO-AP1roG) are assessed against standard quantum chemistry methods. Our study indicates that these new geminal-based approaches provide a cheap, robust, and accurate alternative for the description of bond-breaking processes in closed-shell systems requiring only mean-field-like computational cost. In particular, the spectroscopic constants obtained from OO-AP1roG are in very good agreement with reference theoretical and experimental data.
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ISSN:1089-5639
1520-5215
DOI:10.1021/jp502127v